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t the interpretation, for which the vibronic transitions that were previously assigned to a slightly bent structure of the first excited state needs to be revised and that a full rationalization of the PES spectra would require the explicit inclusion of the nuclear dynamical effects, beyond the Born-Oppenheimer (BO) approximation. From a methodological point of view, the relativistic EOM-IP-CCSD method results are highly accurate and capable of giving a well-balanced description of the anionic and neutral species, which is a key aspect for the interpretation of the PES spectra in open-shell heavy element compounds.Conversion of propane or butanes from natural/shale gas into propene or butenes, which are indispensable for the synthesis of commodity chemicals, is an important environmentally friendly alternative to oil-based cracking processes. Herein, we critically analyse recent developments in the non-oxidative, oxidative, and CO2-mediated dehydrogenation of propane and isobutane to the corresponding olefins over metal oxide catalysts. Particular attention is paid to (i) comparing the developed catalysts in terms of their application potential, (ii) structure-activity-selectivity relationships for tailored catalyst design, and (iii) reaction-engineering aspects for improving product selectivity and overall process efficiency. On this basis, possible directions for further research aimed at the development of inexpensive and environmentally friendly catalysts with industrially relevant performance were identified. In addition, we provide general information regarding catalyst preparation and characterization as well as some recommendations for carrying out non-oxidative and CO2-mediated dehydrogenation reactions to ensure unambiguous comparison of catalysts developed in different studies.The use of WO3 as an acid catalyst has received extensive attention in recent years. However, the correlation between the catalytic activity and the predominantly exposed surface with varied acidic sites needs further understanding. Herein, the effects of the Brønsted and Lewis acid sites of different crystal facets of WO3 on the catalytic conversion of furfuryl alcohol (FA) to ethyl levulinate (EL) in ethanol were investigated in detail. A yield of EL up to 93.3% over WO3 with the (110) facet exposed was achieved at 170 °C, while FA was mainly converted to polymers over (001) faceted nanosheets and nanobelts with exposed (002) and (100) facets. This was attributed to the different distribution of the acidic sites on different exposed crystal facets. The (110) faceted WO3 possessed abundant and strong Brønsted acid sites, which favored the conversion of FA to EL, while the (100) faceted WO3 with stronger Lewis acid sites and weaker Brønsted acid sites mainly led to the formation of polymers. In addition, the (110) faceted WO3 showed excellent sustainability in comparison with the (100) faceted counterpart.A method is proposed to select the suitable sets of potential parameters for a one-dimensional mesoscopic Hamiltonian model, first introduced to describe the DNA melting transition and later extended to investigate thermodynamic and dynamical properties of nucleic acids. The DNA base pair fluctuations are considered as time dependent trajectories whose initial condition sets the no crossing constraint enforced in the path integral for the first-passage probability. Performing the path integration at room temperature, relations are established between the cutoff on the amplitude of the base pair fluctuations and the model parameters. In particular, a suitable range of values for the non-linear stacking parameter has been proposed while the effect of the stiffness constant on the first-passage probability has been highlighted. The formalism here developed may be applied to compute the lifetime of open base pairs in three-dimensional helical models for DNA molecules.Constructing acid-base pairs is one of the efficient strategies for the design of proton conductors with high conductivity, due to the ultrafast proton-hopping with a low energy barrier between a proton donor (acid group) and an acceptor (base group). In this study, an acid-base adduct polyamine-P2Mo5 model system was established, including adducts [C6N4H22][H2P2Mo5O23]·H2O (P2Mo5-TETA), [C4N3H16]2[P2Mo5O23]·H2O (P2Mo5-DETA), and [C2N2H10]2[H2P2Mo5O23] (P2Mo5-EN), (TETA = triethylenetetramine, DETA = diethylenetriamine, EN = ethanediamine). Proton conductivity analyses showed that adduct P2Mo5-EN exhibited the highest proton conductivity 1.13 × 10-2 S cm-1 at 65 °C and 95% RH, which was one and three orders of magnitude greater than those of P2Mo5-DETA and P2Mo5-TETA under the same conditions. Ea values of all three adducts are lower than 0.4 eV, which indicates that their proton transfer is attributed to the Grotthuss mechanism. Combined with visual structure analysis, the proton transport pathways of three adducts are highlighted. Moreover, we use this model system to discuss in detail the effect of pKa, proton density and size of polyamine molecules on the proton conductivity of organic amine-POM adducts.Pyroprotein-based carbon materials produced by heat-treating silk proteins have many potential applications in electronic devices, such as electronic textiles. To further develop potential electronic devices using these pyroproteins, the charge transport mechanism has to be verified. However, the electrical characteristics of the pyroproteins have not been reported yet. In this study, the temperature-dependent charge transport behavior of pyroprotein-based electronic yarns prepared from commercial silks (e-CS yarns) is investigated with respect to various heat treatment temperatures (HTT, 800, 1000, 1200, and 1400 °C). The linear current-voltage properties are shown at a low bias of 100 nA from 9 K to 300 K. The temperature-dependent resistivity of the e-CS yarns can be clearly described by the crossover of 3-dimensional Mott variable range hopping and fluctuation-induced tunneling conduction at the crossover temperature (Tc). These Tc factors are significantly different, due to the structural modulation of the e-CS yarns depending on the HTT, and are characterized by Raman spectroscopy, X-ray diffraction, and transmission electron microscopy. This study is expected to provide a better understanding of the electrical properties of pyroproteins.An atomistic understanding of transition-metal dichalcogenide (TMD) nanoflakes supported on graphene (Gr) plays an important role in the tuning of the physicochemical properties of two-dimensional (2D) materials; however, our current atom-level understanding of 2D-TMD nanoflakes on Gr is far from satisfactory. Thus, we report a density functional theory investigation into the stabilization and binding mechanisms of (MoS2)n/Gr, where n = 1, 4, 6, 9, 12 and 16. We found an evolution of the (MoS2)n…Gr interactions from covalent and hybridization contributions for smaller nanoflakes (n = 1, 4) to vdW interactions for larger (MoS2)n nanoflakes (n ≥ 6); however, the coupling of the (MoS2)n and Gr electronic states for n = 1 and 4 is not intense enough to change the Dirac cones at the Gr monolayer. On average, the 1T’- and 2H-(MoS2)n nanoflakes bind with similar adsorption/interaction energies with Gr, and hence the (MoS2)n…Gr interactions do not change the high energetic preference of the 1T’- structures, which can be explained by the stabilizing role of the S-terminated edges in the 1T’-(MoS2)n in contrast with the destabilizing role of the edges in the 2H-(MoS2)n nanoflakes.Changes in the local structure and magnetic properties at Fe sites due to defects were addressed in a detailed manner in Co2FeAl by 57Fe Mössbauer spectroscopy. Based on the systematic correlation of these results a comprehensive understanding of the defects and hence of the different types of disordering that occur in Co2FeAl subjected to different non-equilibrium treatments have been obtained in this study. As high as 35% of the Fe atoms were deduced to be associated with the A2 type of disordering in Co2FeAl, which provides a basic understanding of the observed much lower value of spin polarization as observed in this system against the high value predicted theoretically. Also this study revealed a striking linear correlation between the valence electron concentration and the effective magnetic hyperfine fields as deduced at different sites of occupation of 57Fe atoms.Adequate knowledge of protein conformations is crucial for understanding their function and their association properties with other proteins. The cataract disease is correlated with conformational changes in key proteins called crystallins. These changes are due to mutations or post-translational modifications that may lead to protein unfolding, and thus the formation of aggregate states. Human βB2-crystallin (HβB2C) is found in high proportion in the eye lens, and its mutations are related to some cataracts. HβB2C also associates into dimers, tetramers, and other higher-order supramolecular complexes. this website However, it is the only protein of the βγ-crystallin family that has been found in an extended conformation. Therefore, we hypothesize that the extended conformation is not energetically favourable and that HβB2C may adopt a closed (completely folded) conformation, similar to the other members of the βγ-crystallin family. To corroborate this hypothesis, we performed extensive molecular dynamics simulations of Hpped dimer (crystallographic structure). The results presented in this report shed light on the molecular details of the folding mechanism of HβB2C in an aqueous environment and may contribute to interpreting different experimental findings. Finally, a detailed knowledge of HβB2C folding may be key to the rational design of potential molecules to treat cataract disease.Bilirubin originates from hemoglobin metabolism and is an important biomarker for liver function. A ratiometric film sensor based on gold nanoclusters (AuNCs) was fabricated for highly sensitive determination of free bilirubin (fBR). Using bovine serum albumin (BSA) as a template, AuNCs that can emit blue and red fluorescence were prepared by the hydrothermal method at different pH values. Two kinds of AuNCs were incorporated into a single film by the layer-by-layer assembly (LBL) technique. The obtained thin-film showed dual fluorescence peaks excited at 372 nm, corresponding to the blue (443 nm) and red (622 nm) emissions of AuNCs respectively. When fBR interacted with the film, both fluorescence peaks were quenched at different degrees. A ratiometric method for fBR detection was established based on the fluorescence intensity ratio of the two emissions. The linear calibration curve for fBR lay in the concentration range of 0.01-2.00 μmol L-1 with a detection limit of 8.90 ± 0.34 nmol L-1 (S/N = 3). The film sensor showed a quick and sensitive response to fBR and could detect fBR in real samples with satisfactory results.A micro fabricated chip-based wearable air sampler was used to monitor the personnel exposure of volatile chemical concentrations in microenvironments. Six teenagers participated in this study and 14 volatile organic compounds (VOCs) including naphthalene, 3-decen-1-ol, hexanal, nonanal, methyl salicylate and limonene gave the highest abundance during routine daily activity. VOC exposure associated with daily activities and the location showed strong agreements with two of the participant’s results. One of these subjects had the highest exposure to methyl salicylate that was supported by the use of a topical analgesic balm containing this compound. Environmental based air quality monitoring followed by the personnel exposure studies provided additional evidence associated to the main locations where the participants traveled. Toluene concentrations observed at a gas station were exceptionally high, with the highest amount observed at 1213.1 ng m-3. One subject had the highest exposure to toluene and the GPS data showed clear evidence of activities neighboring a gas station.